Treatment of textile materials



Patented Aug. 7, 1934 TREATMENT OF TEXTILE MATERIALS CONTAINING CELLULOSE nEaIv TIvss George Rivat, Lyon,

Corporation of Americ ware France, assignor to Celanese a, a corporation of Dela- No Drawing. Application January 12, 1932, Serial No. 586,240. In Great Britain February 11 Claim.

This invention relates to improvements in the coloration or treatment of textile materials made of or containing cellulose esters or ethers, and more particularly in the fixation of coloring matters or pigments in the materials or effecting discharge of colorations thereon.

This application. is in part a continuation of my application No. 517,313, filed February 20, 1931.

As is well known cellulose acetate and other cellulose esters, and in part cellulose ethers, have comparatively limited amnities for a number of well known classes of coloring matters, for example the acid wool colors, direct cotton colors, any of the vat colors, pigments, both white and colored, and also some of the basic dyestuffs. The term coloring matters is hereinafter used in the sense of including not only dyestuffs but also pigments, whether colored or white. This lack of afllnity is especially noticeable in the case of applying the coloring matters by printing or stencilling methods, and the present invention is mainly concerned with processes designed to produce fastcolorations with the aid of coloring matters which normally have little or no amnity for the goods under the conditions of treatment or which hitherto have presented difliculty in their commercial application.

It has been found that if such coloring matters are applied to the materials in the presence of .an organic liquid exerting a solvent or softening action upon the organic derivative of cellulose in the fabric or material, commercially valuable colorations are obtainable despite the lack of ailinity of the coloring matters employed. Preferably such organic liquids are volatile but have a relatively high boiling point.

After the application of the coloring matter together with the organic liquid the fabric or material may be simply dried at an elevated temperature so as to fix the coloring matter. The drying may take place for example at 110150 C. on drying cans, but I prefer to eifect the drying at a temperature below 100 C., for example at a temperature of 80 C. It has been found that the steaming operation commonly applied subsequent to printing and stencilling operations may be eliminated by the process of the present invention. This is obviously of great advantage quite apart from the nature of the coloring matter employed. This process is of considerable advantage in the printing and stencilling of cellulose ester and ether materials with dispersed insoluble colors, for example the SBA, the Cellitone and Duranol colors. These dispersed insoluble colors may, for example, be of the azo series, of the anthraquinone series, for instance amino and amino-hydroxy anthraquinones, and their alkyl or oxy-alkyl derivatives, and nitrated compounds, as for example nitro-diarylamines.

If the fabric or other material to be colored according to the present invention is a delustered fabric, the organic liquid having a solvent or swelling action upon the cellulose derivative relusters the parts of the fabric or material to which it is applied. Thus in the case of printing and stencilling the colors stand out from the delustered ground by reason of the enhanced lustre of the pattern. In some cases and particularly in the case of incorporating the organic liquid in a discharge paste containing zinc formaldehyde sulphoxylate, as hereinafter described, matt effects may be obtained in the printed areas when treating a fabric having normal lustre.

As has been stated above the organic liquid characteristic of the present invention has a solvent or swelling action upon the organic derivative of cellulose on the fabric or material, and preferably is volatile, and has a boiling point above 100 C., and especially between 120 and 180 C. Preferably the organic liquid chosen is one which is readily miscible with the aqueous paste or preparation in which it is incorporated. As examples of suitable liquids I may mention ethyl lactate, diacetone alcohol, diethyl tartrate, dibutyl tartrate, benzyl alcohol and the ethers, esters and ether-esters of glycols, for example ethyl ethylene glycol and methyl'and ethyl glycol mono acetates. Preferably such an organic liquid is present as a comparatively high proportion of the composition applied to the material, for example in a proportion of 20 to 40 or even of a printing paste.

The materials to be treated in accordance with the present invention may consist of or contain any ester or ether of cellulose, for example cellulose acetate, cellulose formate, cellulose propionate, cellulose butyrate. cellulose nitro-acetate, ethyl cellulose, methyl cellulose and benzyl cellulose, the said cellulose derivatives being present alone or in admixture with each other or in admixture with other fibres, for instance cotton, reconstituted cellulose, natural silk or wool. Differential effects are of course obtainable on fabrics containing such other fibres in accordance with the aflinity of the said fibres for the dyestufis or coloring matters applied.

The process of the present invention is particularly valuable in relation to the application of dyestufls having little or no amnity for the goods under treatment, for example the acid or direct dyes in the case of cellulose ester goods. As examples of such acid or direct dyes may be mentioned formyl violet 5BN (color index No. 698), milling green (color index No. 667), chromazurine HB (Durand a Huguenin), cupranil brown B (color index No. 560), alkali blue (color index No. 704), metanil yellow (color index No. 138), milling red G (color index No. 344), milling red B, polar red G conc. (color index No. 430), benzyl green B (color index No. 667), palatine black (color index No. 241) cyanol FFG, milling orange (color index No. 274) acid blue N. V. 8., orange II (color index No. 151), neolan orange R (color index supplement, page 47), induline (color index No. 861), induline brown, acid wool blue N, amacid fast light yellow 2G (color index No. 639), polar brilliant red 3G conc. (Geigy), wool fast blue GL (color index No. 833), sulphoflavine brilliant FF, alkali blue 43 (color index No. 704), indocyanine brilliant G, acid violet 5 BE (color index No. 698) sulpho green J. 80 (color index No. 670), tartrazine (color index No. 640), and cloth red B (color index No. 262).

The invention is of particular importance in the application of direct blacks, for example chloramine black E2B or chloramine black ER extra (both on page 31 of the color index supplement), modern black and modern black N. Other substantive colors which may be employed in accordance-with the present invention are chrysophenine (color index No. 365), chrysophenine Y (color index No. 365), diamine fast scarlet 4B (color index No. 321), cotton blue 3G (color index No. 503). Other dyestuffs may be applied, for example palatine orange (tetranitrodioxydiphenyl) and full green NB.

The invention is further of great importance in the application of vat dyestuffs of the indigoid or anthraquinone series, whether applied as such or in the form of esters of their leuco compounds, for example indanthrene yellow GK (color index No. 1118), algol scarlet G paste (color index No. 1129) or ciba blue 2BD (color index No. 1184) or other similar dyestufls. Furthermore, as already indicated the invention is of importance in the fixation on the materials of pigments, both white and colored, for example Prussian blue, chrome yellow, titanium oxide or titanox, antimony white, lithopone, zinc white or zinc oxide, barium sulphate or blanc-fixe and-ultramarine.

Moreover as has already been stated certain basic dyestuffs present difiiculty in their application to the goods, particularly when applied by printing methods. The present invention envisages the application together with the organic liquids referred to of such dyestuffs, for example chromacetine blue S (color index No. 884). rhoduline blue 6G (color index No. 658) benzyl violet (color index No. 683), induline (color index No. 861), acridine orange (color index No. 788), acridine red PS (color index No. 740), acridine red, rhodamine 3 GO (color index No. 749) rhoduline yellow 6G (color index No. 815), auramine (color index No. 655), fuchsine (color index No. 677), capri blue GON (color index No. 876), rhodamine 6G (color index No. 752), setocyanine (color index No. 663), acridine brown (color index, page 338), rhodamine 3 O0, cyanine brilliant red, chromazurine RB, acridine orange E. S. The invention is further valuable in the application of the aniline black type of coloration to the goods.

In addition to improving the simple application of coloring matters to the fabrics 0r materials, the invention is further of advantage inthe production of white or colored discharge effects upon the materials, the organic liquid being applied together with the discharge or together with the coloring matter, or in the case of colored discharges together with the discharge and coloring matter. The discharge preparations may contain oxidizing agents, such as chlorates or chromates or reducing agents, for example hydrosulphites, sulphoxylates, formaldehyde hydrosulphites or sulphoxylates, stannous chloride, stannous chlorothiocyanate or the like. As in the simple application of color the steaming operation customarily applied after a discharge operation may be eliminated and a simple drying at the appropriate temperature be substituted therefor, except in the case of formaldehyde hydrosulphites or sulphoxylates which require steaming before they produce their reducing effect.

Printing pastes, stencilling preparations or the like may contain any other desired ingredients, for example a thickener of any suitable kind, such as gum arabic, starch, British gum or soluble cellulose ethers or even cellulose esters, and any other desired assistants, as for example ethylene thio-diglycol, diethylene glycol, glycol,

etc.

As has been stated above the process of the invention enables the coloring matters to be fixed or the discharge preparations to become operative upon a simple drying of the fabric or material rather than upon a steaming operation, as is customary in the art. Such a drying is preferably effected below 100 C., for example at a temperature of 50 to 80 C., the drying being effected for example by passage of the materials over heated cans or through a heated atmosphere, Preferably the temperature of the drying or the duration thereof is such as to permit of vaporization of the organic liquid applied. After such drying a short washing with luke warm water may be applied and/or a soaping, for example a soaping with a 0.2 to 0.3% soap solution at 50 C. for to 10 minutes.

In the above description it is indicated that the invention is of greatest importance in the application of coloring matters by printing or stencilling methods whether such coloring matters are applied locally or not. However, the improved absorption of the coloring matters consequent upon the use of the organic liquids characteristic of the invention is of great assistance even in bath treatments with the coloring matters, and such methods of application are included within the scope of the invention. Padding methods and pin roll padding methods are particularly important in this connection.

The following examples illustrate the invention but are not to be considered as limiting it in any way:-

Example I A fabric consisting of cellulose acetate yarn is printed with a paste made as follows:- Dyestufl 10 to grams Glyezine (thio-diglycol) to grams Water 160 grams Ethyl lactate 200 to 600 ccs. Gum arabic thickener (1:1),

collo resin 40:60 or other thickener 400 to 600 grams The dyestuif employed therein may be any of the dyestufis mentioned above.

After printing,

I'll

the fabric is dried at to C. for a sumcient time to permit of the vaporization of the ethyl lactate. A short washing with luke warm water then follows, after which the fabric is soaped at 50 C. for 3 to 5 minutes in a soap solution containing 2 to 3 grams of soap per litre and is finally rinsed. If the original fabric is one which has been delustered by hot soap solution or steaming the printed parts have an enhanced lustre as compared with the ground.

Example II A fabric consisting of cellulose acetate yarn is printed with the following paste:

Grams Diphenyl black base 40 to 50 -Aniline 100 to 120 Ethyl lactate 200 Glacial acetic acid 120 Water and thickener 530 After printing with the above paste the fabric is rapidly dried at 60 to 70 C. and is passed into a bath consisting of a solution havingv the following composition:

Grams Sodium bichromate 15 Water 950 Sulphuric acid of 66 B 33 The fabric is allowed to remain in this bi- Example III A mixed acetate silk viscose fabric is dyed with a diazotized dischargeable color having an affinity for the viscose yarn but not for the cellulose acetate which resists soaping. The fabric is then printed with the following paste:

. Grams Indigosol color 40 to 100 Glyezine 60 Water 230 Formaldehyde hydrosulphite (or in the case of light grounds 150 grams) 200 Gum arabic 1:1 350 Ethyl lactate 150 The fabric is steamed for 6 to 8 minutes in the Mather-Flatt, soaped at 60-70 C. to eliminate the indigosol which has been taken up by the viscose and is then rinsed first in soda and then i with water, and the indigcsol on the acetate silk developed by treatment for 20 minutes at ordinary temperature in a bath containing 2 grams of sodium nitrite and 10 cos. of commercial hydrochloric acid per litre. After development the fabric is rinsed in ordinary water, then in a soda bath and finally in a light soap bath or a bath containing a small amount of sodium acetate.

The fabric has a ground of colored viscose and llulose acetate yarn, while the printed portion consists of colored cellulose acetate and uncolored viscose.

Example IV An acetate silk fabric is printed with the following paste:

Grams Chloramine black ER extra Glyezine 50 Water 200 00110 resin 40:60 400 Ethyl lactate-- 350-400 If the print is carried out on a fabric which has not been delustered 50 to 80 grams of disodium phosphate may advantageously be added to the paste.

Example V A paste is made up as follows:

Modern black N 80 grams Rhoduline yellow 6G--- 20 grams Glyezine 50 grams Collo resin 40:60 400' grams Water 200 grams Ethyl lactate 350-400 ccs.

To this mixture are added 10 grams of sodium hydrosulphite, and the paste is allowed to remain for 24 hours before being printed on a cellulose acetate fabric.

Example VI A mixed cotton-acetate silk oracetate-viscose fabric is printed with a paste made up as follows: V

Acid wool blue N 50 grams Orange 11 10 grams Glyezine 50 grams Water 200 grams Collo resin 40:60 400 grams Ethyl lactate 350-400 ccs.

To this paste 10 grams of cloth red B may advantageously be added.

Example VII A cellulose acetate fabric is grounded by padding or printing with a pin roller with the following bath: a

- Parts Dyestuif 3 Ethyl lactate 30 Glyezine A 10 Water 32 Collo resin 40:60 25 The fabric is then dried at 80 C. as described above, rinsed in lake warm water, soaped at 50- 60 C. for 3-5 minutes in a bath containing 2-3 grams of soap per litre and finally rinsed and dried. It is then printed with the following pastor- Grams Zine formaldehyde sulphoxylate 200 Water 250 Gum arabic 1:1 350 Ethyl lactate 200 It is passed through the Mather-Flatt, washed and dried in the usual manner. By this means a good slightly matt white on the lustrous colored ground is obtained.

Example V!!! A cellulose acetate fabric is minted with a paste made up as follows:

Grams Zinc or titanium oxide British gum 50 Gum arabic 1:1 or collo resin 40:60---- 250-300 Water 300 Ethyl lactate 250 The paste is passed twice through a colloid mill before printing. After printing, drying is effected as already described at 60-70 C., the fabric washed with luke warm water and soaped at about 50 C.

Example IX A cellulose acetate fabric is dyed black (0) by dyeing with 2% of its weight of para-amino-azobenzene-dimethyl-aniline, diazotizing and coupling with 3% of fl-oxy-naphtholic acid. or (b) by means of a direct black with the aid of ethyl lactate as described above. It is then printed with a paste made up as follows:--

Grams Methylene blue 40 Gum arabic 1:1 350 Stannous chloride 200 Ethyl lactate 200 Water 200 Citric acid 10 Example X Grams Glyezine (thio-diglycol) 80 Ethyl lactate 300 to 320 Collo resin (40:60) or other thickener 80 The fabric is then dried at about 70 0., is washed immediately in cold water, and then in warm water (about 50 0.).

Those parts of the fabric to which the second paste has been applied, that is the paste containing the ethyl lactate, have the color that has been applied in the first paste afllxed thereon, while the other parts, not having been treated with the ethyl lactate, are not colored, since the acid colors of themselves have no affinity for the cellulose acetate fabric and are washed away during the washing treatment.

The term mechanical impregnation" as used hereafter in the claims connotes any method of applying a reagent in which, as opposed to a bath treatment process, the whole quantity of reagent is applied to the goods in such an amount of 1,ees,ase

vehicle as can be completely retained by the said loods.

Having now particularly described and ascertained the nature of my said invention and in what manner the same is to be performed. what I claim is:

1. Process of locally coloring materials comprising cellulose eaters or ethers comprising applying thereto a dyestuif having relatively no affinity therefor, and then locally applying thereto an organic liquid exerting a solvent or softening action upon the cellulose derivative, drying, and then washing the material, whereby the parts locally treated are colored and the other parts are not colored.

2. Process of locally coloring materials comprising cellulose acetate comprising applying thereto a dyestufl having relatively no amnity therefor, and then locally applying thereto an organic liquid exerting a solvent or softening action upon the cellulose acetate, drying, and then washing the material, whereby the parts locally treated are colored and the other parts are not colored.

3. Process of locally coloring materials comprising cellulose esters or ethers comprising applying thereto a dyestuil' having relatively no aiiinity therefor, and then locally applying thereto ethyl lactate, drying, and then washing the material, whereby the parts locally treated are colored and the other parts are not colored.

4. Process of locally coloring materials comprising cellulose acetate comprising applying thereto a dyestull' having relatively no aflinity therefor, and then locally applying thereto ethyl lactate, drying, and then washing the material, whereby the parts locally treated are colored and the other parts are not colored.

5. Process according to claim 1, wherein the organic solvent or softener is applied in a proportion of more than 20% of the applied preparation.

6. Process according to claim 3, wherein the ethyl lactate is applied in a proportion of more than 20% of the applied preparation.

7. Process of producing differential color ef- 1 fects on a textile material containing cellulose fibres and cellulose ester or ether fibres, comprising applying thereto by mechanical impregnation a material comprising an ester of a leuco vat dyestuil and an organic liquid exerting a solvent or softening action upon the cellulose derivative,

drying, washing to remove the color from the cellulose fibres only, and then developing the color on the cellulose derivative material.

8. Process of producing diil'erential color effects on a textile material containing cellulose fibres and cellulose ester or ether fibres, comprising applying thereto by mechanical impregnation a material comprising an ester of a leuco vat dyestuil and ethyl lactate, drying, washing to remove the color from the cellulose fibres only, and then developing the color on the cellulose derivative material.

9. Process of producing differential color eflects on a textile material containing cellulose fibres and cellulose ester or ether fibres, comprising applying thereto by mechanical impregnation a material comprising an ester of a leuco vat dyestuf! and ethyl lactate, the ethyl lactate being present in a proportion of more than 20% of the applied preparation, drying, washing to remove the color from the cellulose fibres only, and then developing the color on the cellulose derivative material.

10. Process of producing differential color effects on a textile material containing cellulose lulose fibres only,

facts on a textile material containing cellulose fibres and cellulose ester or ether fibres, comprising applying thereto a material comprising an ester of a leuco vat dyestufi and ethyl lactate, drying, washing to remove the color from the celand then developing the color on the cellulose derivative material.

GEORGE RIVAT. 

